Bis-(beta-oxypropionamido)-alkynes)



United States Patent 3,320,315 BIS-(fi-QXYPROPIQNAMIDW-ALKYNEQ Jack L.Towle, East Cleveland, and Dale G. Block, Cleveland, Ohio, assignors, bymcsne assignments, to Kewanee Oil Company, Bryn Mawr, Pa., a corporationof Delaware No Drawing. Filed Aug. 31, 1964, Ser. No. 393,403 6 Claims.(Cl. 260-561) ABSTRACT OF THE DISCLOSURE The invention comprises newcompounds having an acetylenic bond therein and suitable as additives inelectroplating baths comprising the reaction product of an unsaturatedcarboxamide and an acetylene diol. The simplest of these compounds isprepared by the reaction of butynediol with acrylamide. More complexcompounds are prepared by forming the ethylene oxide derivatives of thediol prior to the reaction with the unsaturated carboxamide.

This invention relates generally to triple bond-containing diamidesuseful as additives in electroplating baths. More particularly theinvention relates to the reaction product of an unsaturated carboxarm'deand a triple bondcontaining diol.

The reaction products comprising the present invention may be describedas alkyneoxyalkanoic diamides and alkadiyneoxyalkanoic diamides. Thesecompounds may be represented by the following general formula.

wherein n is an integer ranging from 0 to inclusive, A represents amember selected from the group consisting of ethylene (CEC) anddiethynylene and when n is 0 R represents hydrogen and R representshydrogen and an alkyl radical having from 1 to 2 carbon atoms. When n is1 to 20, R and R may represent hydrogen and an alkyl radical having from1 to 2 carbon Basic catalyst Com-pounds of the class defined by FormulaI have been found to produce leveling when employed with an aqueous acidsolution of nickel salts capable of supplying nickel ions such as, forinstance, the familiar all chloride, all sulfate, sulfate-chloride orWatts type, nickel fluoroborate, nickel sulfamate types and combinationsthereof. Moreover the diamides of the present invention 3,320,315PatentedMay I6, 1967 ICC characteristically do not cause on the articleto be plated.

In general, the compounds of the present invention are advantageouslyemployed as levers in concentrations in the range of from about .005g./l. to about 1.0 g./l. Within this broad concentration range there arethree more limited ranges wherein the limits are determined by the typeof cooperating additives employed with the leveler and by the type ofnickel coating desired. When the compound is employed as a leveler alonein a nickel plating bath without the use of cooperating compounds, thecompound preferably is present in the range of from about .005 g./l. toabout 0.1 g./l. When the compound is employed as a leveler in a nickelplating 'bath containing cooperating compounds for purposes of obtaininga semibright nickel plate, the compound preferably is present in therange of from about .01 g./l. to about 0.3 g./l. When the compound isemployed in a nickel plating bath containing cooperating compounds forpurposes of obtaining a bright nickel plate, the compound preferably ispresent in the range of from about .05 g./l. to about 1.0 g./l.

Increased leveling and more uniform lustre are obtained with the instantcompounds when they are employed in combination with a secondcooperating compound. The cooperating compound is define'd as a trihaloaldehyde or acetal or hemiacetal precursor thereof.

Specific examples of the cooperating compounds include 1,1diethoxy-2,2,2-trichloroethane, 1-hydroxy-1-e.thoxy2,2,2-trichloroethane, l,1-dimethoXy-2,2,2-trichloroethane,1-hydroxy-l-methoxy 2,2,2 trichloroethane, 1,1dirnethoxy-2,2,2-triboromethane, trichloroethanal, and tri=bromoethanal.

In general, these cooperating compounds when present in the semi-brightplating solutions are employed advantageously in concentrations in therange of from about 0.01 gram per liter to about 2.0 grams per liter.Tri chloroethanal, an especially useful cooperating compound, may beused to advantage in the semi-bright platings solution in concentrationsin the range of from about 0.01 gram per liter to about 0.5 gram perliter, .and preferably in the range of from about 0.03 gram per liter toabout 0.1 gram per liter.

In general, the compounds of this invention are prepared by dissolvingthe acetylenic diol and the amide in a suitable solvent and adding therequired amount of alkaline catalyst such as an aqueous solution oftrimethyl benzyl ammonium hydroxide, aqueous potassium hydroxide orsodium tertiary butoxide. The quantity of catalyst required is in therange of from about'l percent to about 20 percent by weight of thecombined weights of the reactants. In addition to the catalystsmentioned, any agent capable of promoting a Michael reaction would servein these reactions. Other suitable catalysts for use in carrying out theMichael reaction include alkali-metal alkoxides, -aryl and -amides.

The preferred solvent is tertiary butanol but other compounds free ofhydrogen atoms capable of undergoing conjugate addition reactions may beused, such as dioxane, tetrahydrofuran, 1,2-dimethoxyethane and thelike. The compound should be liquid at room temperature (25 C.) andsubstantially inert to the reactants and the catalysts.

The reaction takes place readily at temperatures in the range of fromabout 25 C. to about C., although temperatures in the range of fromabout 40 C. to about 70 C. are preferred. The reaction period is notcritical; periods ranging from 3 to 16 hours may be used, although mostreactions are completed within periods ranging from 4 to 8 hours.

When the reaction is completed, the product may be isolated and purifiedby recrystallization from solvents such as methyl or ethyl alcohol.

misplate or skipped areas Specific acetylenic diols suitable asreactants for preparing the compounds of the present invention include3- hexyne-1,6-diol, 2-pentyne-1,5-diol, 2-butyne-1,4-diol and2,4-hexadiyne-1,6-diol. These acetylenic diols are also advantageouslyreacted with up to 20 moles and preferably not more than moles ofethylene oxide per hydroxyl group. These reaction products being diolsthemselves may be reacted with the a,;8-ethylenically unsaturated amide.The original diol may contain secondary hydroxyl groups which can bereacted with ethylene oxide. The hydroxyl groups preferably should be onthe second or third carbon atom from the end of the alkyne chain.Moreover the original diol may be a tertiary diol if it is first reactedwith ethylene oxide in the manner disclosed by K. D. Petrov and E. S.Laguchevu, Zhur. Obshchei Khim., 21, 1247 (1951), CA. 46, 1959.

The amides employed have the general formula:

0 oHi=oH-( i-NHz wherein Z is hydrogen, methyl or hydroxymethyl group.

Specific amides which have been found suitable for purposes of thisinvention are acrylamide, N-methylacrylamide andN-hydroxymethylacrylamide.

These following examples are given for purposes of illustration and notby way of limitation. All parts and percentages are by weight unlessotherwise specified.

EXAMPLE I 1 ,4-bis( 3-oxy propionamid e) butyne-Z In a one liter3-necked flask equipped with stirrer, thermometer and reflux condenseris placed 325 g. of tertiary butanol. The alcohol is heated to 40 C. and43 g. (0.5 mole) 2-butyne-1,4-diol, 71.5 g. (1.01 moles) acrylamide and7.2 g. of 40% aqueous potassium hydroxide is added in that order. Thecloudy orange solution is filtered through Filter-cel and the clearorange filtrate heated with stirring at 45 C.50 C. for eight hours.After one hour, the product begins to separate from solution and soonthe reaction mixture is a thick creamcolored mass.

At the end of eight hours, the mixture is cooled to 30 C., filtered andthe pale brown solid dried to constant weight in an oven at 80 C. Thecrude yield is 104 g. (91.2%) melting at 112 C.-118 C.

The crude product is dissolved in 325 g. of hot absolute methanolcontaining 1 g. of activated carbon, heated for 15 minutes and filtered.The orange filtrate is cooled to 20 C. and the crystals which separatedare filtered and dried. The product weighs 74 g. (overall yield of 65%)and melts at 132 C. to 133 C. The elemental analysis, molecular weightdeterminations and infrared absorbencies of the product are as follows:Calculated for C H N O C, 52.62; H, 7.07; N, 12.27; mol. wt. 228. Found:C, 53.00; H, 6.91; N, 12.29; mol wt. ebullioscopic in ethanol, 228; inbutanone, 232.

m (a) 3.43, 3.47 (CH2); 2.98, 3.15 (amide NH); 6.02, 6.07, 6.20 (amideC=O), 8.97, 9.22, 9.37 (o o-o EXAMPLE II1,4-bis(fl-0xypropionamide)butyne-Z A mixture of 28.4 g. (0.4 mole) ofacrylamide, 17.2 g. (0.2 mole) of 1,4-butynediol and 200 g. of tertiarybutyl alcohol is stirred at 50 C. until a clear solution is obtained. Tothis is added a slurry of sodium tertiarybutoxide prepared from 2 g. ofsodium and 24 g. of tertiary butyl alcohol and the mixture stirred at 45C.50 C. for eight hours and then allowed to stand at room temperaturefor an additional hours. The resulting thick slurry is then added to 800g. of ethyl ether, mixed thoroughly, and filtered. The crude product isrecrystallized from anhydrous methanol to give 24.5 g. (63.3%) of1,4-bis(/3oxypropionamide)butyne-2, melting at 133 c.-134 c.

The infrared absorbancies are as follows:

RE; (;1) 3.43, 3.47 (CH 2.98, 3.15 (amide NH), 6.02, 6.07, 6.20 (amideC=O), 8.97, 9.22 9.37, (C-O-C) EXAMPLE III1,4-bis(N-methyl-fl-oxypropionamide)butyne-Z To 59.3 g. tertiary butanolis added 8.6 g. (0.1 mole) 1.4-butynediol and then heated with agitationuntil solution is complete. At 35 C.40 C. is added 17.0 (0.2 mole)N-methylacrylamide followed by 5.0 g. 50% aqueous benzyltrimethylammonium hydroxide (Triton B). A nitrogen atmosphere is provided and thetemperature raised to 45 C.50 C. and maintained at this temperature fora period of eight hours during which time the reaction mixture iscontinuously agitated. At the end of this time, the mixture istransferred to a separatory funnel and extracted with two 200 ml.portions of petroleum ether (B.P. 30 C.-60 C.) to remove the tertiarybutanol. The brown oil that remains subsequent to the petroleum etherextraction partially crystallizes. The crystals that separate are washedfree from the brown oil with successive 50 ml. portions of petroleumether. The crystalline product collected is recrystallized from dioxaneto give a product that melts at 104 C.-105 C. and weighs 7.0 g.

The infrared absorbancies are as follows:

xfi; (,0) 3.35 (CH2); 3.35 (amide NCH3); 3.00 (amide NH), 5.95, 6.07(amide C=O), 8.88, 9.24. (C'-OC).

EXAMPLE IV 1,6-bis(;8-0xypr0pionamide)hexadiyne-2,4

In a 500 ml. 3-necked flask equipped with a stirrer, thermometer andreflux condenser is placed a mixture of 11 g. (0.1 mole)2,4-hexadiyne-1,6-diol, 14.3 g. (0.202 mole) acrylamide and 2.9 g. 40%aqueous benzyl trimetllyl ammonium hydroxide (Triton B) in 148 g.tertiary butanol. The mixture is stirred at 45 C.50 C. for eight hoursand then allowed to stand at room temperature overnight. A small amount(1.5 g.) of black material is filtered off, and the clear deep redfiltrate is slowly poured with stirring into one liter of ethyl ether.An orange brown gum separates but on further stirring solidifies to asolid brown mass. This solid is recrystallized twice from 95% ethanol togive gray plates (which turned purple on drying) melting at 129 C. to134 C. A mixed melting point with 2,4-hexadiyne-1,6-diol (M.P. 110 C.113C.) is C. C. The compound is soluble in hot water, and the infraredspectrum showed characteristic frequencies for the ether and amidelinkages.

The infrared absorbancies are as follows:

a (;1.) 3.40, 3.50 (CH2), 2.90, 3.12 (amide NH), 5.88,

max.

6.00 (amide C=O), 9.08, 9.18 (COC) EXAMPLE V 1 ,4 -bis (N-hydr0xymethyl-B-0xy propionamide) butyne-Z A (1) 3.42, 3.47 (CH2);2.88, 9.45, 14.30 (alkyl OH);

3'70" (amide NH); 6.02 (amide 0:0); 8.80, 9.10

(COC) EXAMPLES VI AND VII As mentioned hereinbefore the unsaturateddiols may be reacted with up to about 20 moles of ethylene oxide perhydroxyl of the diol. The following examples give the preparation ofsuch products.

Ethylene oxide adduct of 2-bulylze-L4-di0l pounds. The plating solutionmay also contain an antipitting agent, although the deposits may besuitable without the antipitting agent.

Sodium lauryl sulfate or other wetting agents such as Into a 1 lite-r3-necked flask containing 354 grams of 5 the sodium sulfate derivativeof 7-ethyl-2-methyl-undeisopropanol is charged 14 grams of potassiumhydroxide canol-4 and the dihexyl ester of sodium sulfosuccinic acid and21.5 grams (0.25 mole) of 2-butyne-1,4-diol. 110.0 and the like may beused as an antipitting agent. grams (2.5 mole) of ethylene oxide is thenadded to the Preferred concentration ranges for preferred comfiask, andthe resulting solution turns a dark brown. pounds are given in thefollowing table designated as After 5 /2 hours at reflux temperature thesolution is Table I. cooled and filtered through a sintered glassfilter, leaving Specific examples of the electroplating solutionsconpractically no residue. With a second filtering through tainingdifferent cooperating additives are illustrated in the TABLE IConcentration Range Semi-Bright Bright leveler Leveler leveler plus pluscooperatalone, cooperating ing compound,

g./l. compounds, g./l.

(l) NH COCHzCHzOCHgC C-CHgOCHzCHzCONHz lfl bi sw-ogypropionamide) .Ol.04.03. 10 .1-.5 2 NHzCO(CHzCHzO)tCHzC CCHzC(OCH2CH2)eCONH2 w,w liciirbamyll,4-bis .01-.04 .03-. 10 .1-.5

ghftxagxgethylenefl (3) NHzCOCHgCHzOCHzO C-C CCHQOOHgCHzCONHg ldil-bisgifi oxygrgpionamide) .025-.1 .05-.30 .25-.7 (4) HOCHzNHCOCHzCHzOCHzCCCHzOCHzOHZCONHCHQOH" lgii oir iigdiox meth i- .0l.06 .03-.20 .1-1.o

ggtxgggpionamide) (5). CHgNHCOCHaCHzOCHzC CCHzOCHzCHzCONHCHa1,4-bis(N-niethyl-fi-oxy- 01-.06 .03-.2o

. propionamide)butyne-2.

activated carbon (Nuchar) the filtrate becomes light preceding table. Itshould be understood that the specific brown in color. The isopropanolis then stripped from electroplating solutions may be employed with orwiththe filtrated reaction mass leaving an oily light brown out airagitation. product. The resulting product is ethoxylated Z -butyne-TABLE 1,4-diol having on the-average about five moles of ethylene oxideper hydroxyl group. N}SO4'6H2O 40 Another ethylene oxide adduct of2-butyne -1,4-diol is 2 2 8 6 prepared following substantially the aboveprocedure, but 3 3 using 4 times as much ethylene oxide. The resultingPH product has substantially the same appearance as the Tempellamre 140product of Example VI but is more viscous. Current denslty 45 EXAMPLESVIII AND IX (1) To the basic solution of Example 1 is added:

NH COCH CH OCH C Basing the molecular weights of the products of Ex- EC.CH2OCH2CH2CONH2 1 Q07 amples VI and VII on the amount of ethylene oxideused Trichmmethanal 1 1 in the reaction, respective amounts ofacrylamide are reacted with these products in accordance With the pro-(2) To the basic nickel solution of Example 1 is added: cedure outlinein Example I. The resulting diamides NH2CO(CH2CH2O)3CH2C may berepresented by the general formula designated as =CCH (OCH CH CONH A 015 I (supra) wherein n is 5 and 20 respectively for the two 2 2 2 3 2products.

The acetylenic diamides of the present invention ad- (3) APlatmg sohmoncontammg' vantageously may be used in a bath comprising Nlclfelfiuombofate 45 (1) Water Bonc acid oz./gal 4 (2) A source of nickel ionscomprising at least one P 3.0 nickel salt selected from the groupconsisting of: nickel Temperature sulfate, nickel chloride, nickelsulfamate and nickel fiuoro- 2 2 2 2 bofate g./l

(3) One of the hereinbeforementioned cooperating Trichlofoethanal --g.L- 11 compounds.

(4) A Wetting agent (optional) (4) Plating solution containing.

An additional ingredient of the solution which is de- Nickel sulfamate0z./gal 45 sirable is a buffering agent such as boric acid, formic acid,7 Nickel chloride ..oz./gal 1 sodium formate and the like. pH 4.0

As mentioned hereinbefore the basic nickel-containing Temperature Fsolutions advantageously contain one or more of the com- NH COCH CH OCHC pounds of the present invention and preferably one orECCECCH2OCH2CH2CONH2 g./l 0.2 more of the hereinbefore mentionedcooperating com- 7 Trichloroethanal g./l 0.1

While the foregoing electroplating baths are prepared in concentrationsand employed at current densities for the electrodeposition thereof.When a bright nickel deposit is desired, the compound or leveling agentof the present invention should be employed in concentrations of fromabout .05 gram per liter to about 1.0 gram per liter. Moreover thecompounds may advantageously be employed with the hereinbefore mentionedcooperating addition agents.

The compounds of the present invention have been found to be suitablefor electrodepositing nickel upon any of the basis metals commonlyemployed in the electroplating art, such as, for example, iron, steel,copper, brass and zinc. It has been found, however, that the compounds(leveling addition agents) of this invention and particularly when theleveling addition agent of this invention is employed in conjunctionwith the cooperating addition agent enhanced nickel electrodeposits areobtained on zinc die castings. The zinc basis metal is, of course,preferably subjected to those pretreatment operations common to the artof electroplating prior to the deposition of nickel from the nickelplating bath of this invention. The coating of zinc basis metal withcopper is commonly done prior to electrodeposition of nickel. Ingeneral, the degree of leveling obtained through the deposition of asemi-bright plate of this invention is from about 20 percent to about 50percent for 1 mil deposits. The percentage of leveling is defined asdecrease in roughness due to plating initial roughness of basis metal AR HOH wherein n is an integer ranging from 0 to 20 inclusive, Arepresents a member selected from the group consisting of ethynylene anddiethynylene, and when n is 0, R represents hydrogen and R represents amember selected from the group consisting of hydrogen and alkyl havingfrom 1 to 2 carbon atoms, and when n is 1 to 20, R and R represent amember selected from the group consisting of hydrogen and alkyl havingfrom 1 to 2 carbon atoms, and Z represents a member selected from thegroup consisting of hydrogen, methyl and hydroxymethyl.

2. The compound represented by the formula: NH COCH CH OCH CECCH OCH CHCONH 3. The compound represented by the formula: NH CO CH CH O CH CE CCH(OCH CH CONH 4. The compound represented by the formula: NH COCH CH OCHCECC ECCHZOCHZCHZCONHZ 5. The compound represented by the formula:

HOCH NHCOCH CH OCH C E CCH OCH CH CONHCH OH 6. The compound representedby the formula: CH NHCOCH CH OCH CECCH OCH CH CONHCH No referencescited.

ALEX MAZEL, Primary Examiner.

JOSEPH A. NARCAVAGE, Assistant Examiner.

1. A CLASS OF COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULA